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Crystals 2016, 6(5), 57; doi:10.3390/cryst6050057

Article
The Synthesis and Crystal Structure of Two New Hydrazone Compounds
1
College of Information and Engineering, Weifang University, Weifang 261061, China
2
College of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, China
*
Author to whom correspondence should be addressed.
Academic Editor: Helmut Cölfen
Received: 18 March 2016 / Accepted: 12 May 2016 / Published: 17 May 2016

Abstract

: Two new hydrazone compounds, 4-formylimidazole-4-hydroxybenzhydrazone dihydrate (1) and 2-nitrobenzaldehyde-2-furan formylhydrazone (2), were synthesized via the classical synthesis method. Their structure was determined via elemental analysis and X-ray single crystal diffraction analysis. Compound 1 crystallizes in triclinic, space group P-1 with a = 7.0321(14) Å, b = 7.3723(15) Å, c = 13.008(3) Å, α = 98.66(3)°, β = 101.69(3)°, γ = 92.25(3)°, V = 651.2(2) Å3, Z = 2, Dc = 1.358 g·cm−3, μ = 0.106 mm−1, F(000) = 280, and final R1 = 0.0564, wR2 = 0.1420. Compound 2 crystallizes in monoclinic, space group P21/c with a = 17.3618(9) Å, b = 9.1506(4) Å, c = 15.5801(7) Å, β = 104.532(5)°, V = 2396.05(19) Å3, Z = 8, Dc = 1.437 g·cm−3, μ = 0.111 mm−1, F(000) = 1072, and final R1 = 0.0633, wR2 = 0.1649. Compound 1 forms a 2D-layered structure via the interactions of 1D chains and Compound 2 forms a 3D network structure via the interactions of 1D chains.
Keywords:
hydrazone compound; crystal structure; characterization

1. Introduction

Hydrazone compounds (–NH–N=C–) and their complexes have been widely studied due to their facile synthesis and potential biological activities [1,2,3,4,5]. During recent years, many hydrazone compounds and their complexes have displayed novel structures and extensive applications in luminescent probes, antibacterial and antitumor agents, fluorescence markers, optical materials, and anticonvulsant agent [6,7,8,9,10,11]. In the past ten years, we have done some work in the synthesis, structural characterization, and properties of hydrazone compounds, which show novel structures and luminescent properties [12,13,14,15,16]. In this paper, two new hydrazone compounds have been synthesized via the classical synthesis method, and their crystal structures have also been determined by X-ray single crystal diffraction analysis. The schemes of the compounds are given in Figure 1.

2. Results and Discussion

Description of Compounds 1 and 2

The molecular plots of Compounds 1 and 2 with the atomic labeling scheme are given in Figure 2. Compound 1 is of an almost coplanar configuration with a dihedral angle of 2.5° between Plane 1 (C9–N3–C10–N4–C11) and Plane 2 (C1–C2–C3–C4–C5–C6). The crystal structure analysis shows that Compound 1 contains two lattice water molecules. From the bond length data, it can be seen that the C8–N2 bond length of 1.2760(17) Å is shorter than that of C7–N1 (1.3464(16) Å), which indicates that the bond of C8–N2 is a double bond. Moreover, the C7–O2 bond length of 1.226(2) Å is shorter than that of C3–O1 (1.3537(16) Å), which indicates that the bond of C7–O2 is also double bond.
The dihedral angles between Plane 1 (C1–C2–C3–C4–O1) and Plane 2 (C7–C8–C9–C10–C11–C12) is 26.2°, and that of Plane 3 (C19–C20–C21–C22–C23–C24) and Plane 4 (C13–C14–C15–C16–O5) is 35.5° in Compound 2. From the bond length data, it can be seen that the bond lengths of C6–N2 (1.267(4) Å) and C18–N5 (1.264(4) Å) are shorter than those of C5–N1 (1.337(4) Å) and C17–N4 (1.352(4) Å), which indicates that the bonds of C6–N2 and C18–N5 are double bonds. Moreover, the bond lengths of C5–O2 (1.234(4) Å) and C17–O6 (1.221(4) Å) are shorter than those of C3–O1 (1.361(4) Å), C4–O1 (1.358(4) Å), C13–O5 (1.360(4) Å), and C16–O5 (1.355(4) Å), which indicates that the bonds of C5–O2 and C17–O6 are also double bonds. The bond lengths and bond angles of two molecules in each asymmetric unit are different.
The bond lengths and bond angles in Compounds 1 and 2 are in accordance with the results in [17,18].
Bonds for 1: C3–O1 1.3537(16) Å; C7–O2 1.2389(16) Å; C7–N1 1.3464(16) Å; C8–N2 1.2760(17) Å; C9–N3 1.3677(18) Å; C10–N4 1.311(2) Å; C10–N3 1.3376(18) Å; C11–N4 1.3692(18) Å; N1–N2 1.3786(14) Å; C1–C2 1.3810(19) Å; C1–C6 1.3985(17) Å; C2–C3 1.376(2) Å; C3–C4 1.390(2) Å; C4–C5 1.3824(18) Å; C5–C6 1.384(2) Å; C6–C7 1.4869(16) Å; C9–C8 1.4441(16) Å; C9–C11 1.3675(18) Å.
Bonds for 2: C4–O1 1.358(4) Å; C3–O1 1.361(4) Å; O2–C5 1.234(4) Å; N3–O3 1.218(4) Å; N3–O4 1.229(4) Å; C5–N1 1.337(4) Å; N1–N2 1.388(3) Å; C6–N2 1.267(4) Å; C12–N3 1.471(4) Å; C1–C4 1.328(4) Å; C1–C2 1.413(4) Å; C2–C3 1.330(5) Å; C4–C5 1.472(4) Å; C6–C7 1.460(4) Å; C7–C8 1.393(4) Å; C7–C12 1.402(4) Å; C9–C8 1.370(5) Å; C9–C10 1.373(5) Å; C10–C11 1.374(5) Å; C11–C12 1.374(5) Å. C16–O5 1.355(4) Å; C13–O5 1.360(4) Å; O6–C17 1.221(4) Å; N6–O7 1.187(5) Å; N6–O8 1.160(5) Å; C17–N4 1.352(4) Å; N4–N5 1.376(3) Å; C18–N5 1.264(4) Å; C24–N6 1.457(5) Å; C13–C14 1.304(6) Å; C14–C15 1.412(5) Å; C15–C16 1.323(5) Å; C16–C17 1.461(4) Å; C18–C19 1.475(4) Å; C19–C24 1.387(5) Å; C19–C20 1.388(5) Å; C20–C21 1.373(5) Å; C21–C22 1.364(6) Å; C22–C23 1.369(6) Å; C23–C24 1.378(5) Å.
Angles for 1: C2–C1–C6 121.09(13)°; C3–C2–C1 120.34(12)°; O1–C3–C2 123.0(12)°; O1–C3–C4 117.66(14)°; C2–C3–C4 119.33(12)°; C3–C4–C5 120.15(14)°; C4–C5–C6 121.26(12)°; C5–C6–C1 117.83(12)°; C5–C6–C7 124.14(11)°; C1–C6–C7 118.03(12)°; O2–C7–N1 120.93(11)°; O2–C7–C6 121.83(11)°; N1–C7–C6 117.24(11)°; N2–C8–C9 119.40(12)°; C11–C9–N3 105.80(12)°; C11–C9–C8 129.66(13)°; N3–C9–C8 124.55(11)°; N4–C10–N3 111.96(14)°; C9–C11–N4 109.42(13)°; C7–N1–N2 117.51(11)°; C8–N2–N1 116.19(11)°; C9–N3–C10 107.19(12)°; C10–N4–C11 105.64(12)°.
Angles for 2: C4–O1–C3 106.1(3)°; C5–N1–N2 120.0(3)°; C6–N2–N1 114.2(3)°; O3–N3–O4 124.6(3)°; O3–N3–C12 117.8(3)°; O4–N3–C12 117.5(3)°; C4–C1–C2 106.9(3)°; C3–C2–C1 106.3(3)°; C2–C3–O1 110.4(3)°; C1–C4–O1 110.3(3)°; C1–C4–C5 132.0(3)°; O1–C4–C5 117.7(3)°; O2–C5–N1 124.4(3)°; O2–C5–C4 120.3(3)°; N1–C5–C4 115.3(3)°; N2–C6–C7 120.5(3)°; C8–C7–C12 116.2(3)°; C8–C7–C6 121.0(3)°; C12–C7–C6 122.6(3)°; C9–C8–C7 121.7(3)°; C8–C9–C10 120.1(3)°; C9–C10–C11 120.6(3)°; C10–C11–C12 118.7(3)°; C11–C12–C7 122.6(3)°; C11–C12–N3 116.8(3)°; N3–C12–C7 120.6(3)°. C16–O5–C13 106.4(3)°; C17–N4–N5 119.0(2)°; C18–N5–N4 115.7(3)°; O8–N6–O7 119.2(5)°; O8–N6–C24 119.1(5)°; O7–N6–C24 121.0(4)°; C14–C13–O5 110.5(3)°; C13–C14–C15 106.5(4)°; C16–C15–C14 107.2(3)°; C15–C16–O5 109.3(3)°; C15–C16–C17 134.5(3)°; O5–C16–C17 116.1(3)°; O6–C17–N4 123.7(3)°; O6–C17–C16 121.7(3)°; N4–C17–C16 114.6(3)°; N5–C18–C19 118.7(3)°; C24–C19–C20 116.1(3)°; C24–C19–C18 125.0(3)°; C20–C19–C18 119.0(3)°; C21–C20–C19 122.0(4)°; C22–C21–C20 120.1(4)°; C21–C22–C23 120.0(4)°; C22–C23–C24 119.3(4)°; C23–C24–C19 122.5(4)°; C23–C24–N6 117.0(4)°; N6–C24–C19 120.5(3)°.
The molecules of both Compound 1 and Compound 2 form a 1D-chained structure via the intermolecular hydrogen bonds (N–H...O) (Figure 3). In addition, Compound 1 forms a two-dimensional layered structure via the interactions of 1D chains (Figure 4). Furthermore, Compound 2 forms a three-dimensional network structure via the interactions of 1D chains (Figure 4).

3. Experimental Section

3.1. Materials and Instrumentation

4-formylimidazole, 2-nitrobenzaldehyde, 4-hydroxybenzhydrazine, and 2-furan formylhydrazine were purchased from the Xiya Reagent Company. The analyses of C, H, and N were made on an Elementar Vario EL III elemental analyzer (Elementar, Hanau, Germany). IR spectra were recorded as KBr pellets with a Nicolet AVATAR 360 FTIR spectrometer (Nicolet Instrument Inc., Madison, WI, USA) in the 4000~400 cm−1 region. 1H NMR spectra were recorded on a Bruker Avance-400 spectrometer (Bruker, Elisabethhof, Netherlands) with C2D6OS as the solvent. The X-ray single-crystal data collection for the hydrazone compounds 1 and 2 were performed on a Bruker Smart-1000 CCD diffractometer (Bruker, Billerica, MA, USA).

3.2. Preparation of Two Hydrazone Compounds

4-formylimidazole-4-hydroxybenzhydrazone dihydrate (1): 0.0961 g 4-formylimidazole (1.0 mmol) and 0.1522 g 4-hydroxybenzhydrazine (1.0 mmol) were dissolved in 10 mL of 95% CH3CH2OH. The mixture was refluxed for 5 h. Then, the solution was filtered. The colorless crystals of 4-formylimidazole-4-hydroxybenzhydrazone dihydrate were obtained from the above filtrate via slow evaporation at room temperature for 5 days. Elemental analysis calc. for C11H14N4O4: C, 49.58, H, 5.26, N, 21.03(%); Found: C, 49.32, H, 5.65, N, 21.43(%). IR: 3452 cm−1 (O–H and N–H), 1639 cm−1 (C=O), 1592 cm−1 (C=N). 1H NMR (ppm): 14.22 (s, 1H, –OH), 12.81 (s, 1H, –NH–), 8.01 (s, 1H, –CH=N), 7.85 (d, 2H, Ar–H), 7.63 (s, 1H, imidazol–H), 7.45 (s, 1H, imidazol–H), 6.90 (d, 2H, Ar–H).
2-nitrobenzaldehyde-2-furan formylhydrazone (2): 0.1511 g 2-nitrobenzaldehyde (1.0 mmol) and 0.1261 g 2-furan formylhydrazine (1.0 mmol) were dissolved in 15 mL of 95% CH3CH2OH. The mixture was refluxed for 5 h. Then, the solution was filtered. The yellow crystals of 2-nitrobenzaldehyde-2-furan formylhydrazone were obtained from the above filtrate via slow evaporation at room temperature for 15 days. Elemental analysis calc. for C12H9N3O4: C, 55.55, H, 3.47, N, 16.20(%); Found: C, 55.32, H, 4.26, N, 15.81(%). IR: 1640 cm−1 (C=O), 1593 cm-1 (C=N). 1H NMR ( ppm): 12.23 (s, 1H, N–H), 8.87 (s, 1H, –CH=N), 8.10 (m, 2H, Ar–H), 7.94–8.02 (m, 1H, furan–H), 7.83 (t, 1H, Ar–H), 7.62–7.74 (m, 1H, Ar–H), 7.36 (s, 1H, furan–H), 6.73 (dd, 1H, furan–H).

3.3. Crystal Structure Determination

The important crystal data of Compound 1 and Compound 2 are listed in Table 1. Diffraction data of both Compound 1 and Compound 2 were collected at 293 (2) K on a Bruker Smart-1000 CCD diffractometer by using a φ~ω scan mode. The structures were solved via direct methods with SHELXL-97 program package [19] and refined with SHELXTL-97 [20].

4. Conclusions

Two new hydrazone compounds, 4-formylimidazole-4-hydroxybenzhydrazone dihydrate (1) and 2-nitrobenzaldehyde-2-furan formylhydrazone (2), were synthesized via classical synthesis method. Their structures were determined via elemental analysis and X-ray single crystal diffraction analysis. The results show that Compound 1 forms two-dimensional layered structure via the interactions of 1D chains. And Compound 2 forms three-dimensional network structure via the interactions of 1D chains.

Supplementary Materials

The following are available online at https://www.mdpi.com/2073-4352/6/5/57/s1. Figure S1: IR spectrum of compound 1; Figure S2: IR spectrum of compound 2; Figure S3: 1HNMR spectrum of compound 1; Figure S4: 1HNMR spectrum of compound 2. CCDC 1456984 (1) and 1469125 (2) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336033; E-mail: [email protected]).

Acknowledgments

This project was supported by the National Natural Science Foundation of China (No. 21171132), the National Natural Science Foundation of Shandong (ZR2014BL003), the Project of Shandong Province Higher Educational Science and Technology Program (J14LC01), and the Science Foundation of Weifang.

Author Contributions

Wang Li-Hua synthesized Compound 1 and Compound 2. Tai Xi-Shi designed the experiments and wrote the manuscript.

Conflicts of Interest

The author confirms that this article content has no conflict of interest.

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Figure 1. The scheme of the hydrazone compounds (1 and 2).
Figure 1. The scheme of the hydrazone compounds (1 and 2).
Crystals 06 00057 g001 1024
Figure 2. The molecular structure of Compounds 1 and 2.
Figure 2. The molecular structure of Compounds 1 and 2.
Crystals 06 00057 g002 1024
Figure 3. 1D-chained structure of Compounds 1 and 2 via hydrogen bonds.
Figure 3. 1D-chained structure of Compounds 1 and 2 via hydrogen bonds.
Crystals 06 00057 g003 1024
Figure 4. 2D-layered structure of Compound 1 and 3D network structure of Compound 2.
Figure 4. 2D-layered structure of Compound 1 and 3D network structure of Compound 2.
Crystals 06 00057 g004 1024
Table 1. Crystal data for 1 and 2.
Table 1. Crystal data for 1 and 2.
FormulaC11H14N4O4C12H9N3O4
Formula weight266.26259.22
Crystal systemtriclinicmonoclinic
Space groupP-1P21/c
a [Å]7.0321(14)17.3618(9)
b [Å]7.3723(15)9.1506(4)
c [Å]13.008(3)15.5801(7)
α [°]98.66(3) 90.00
β [°]101.69(3)104.532(5)
γ [°]92.25(3)90.00
Z28
F(000)280 1072
Temperature [K]293(2)293(2)
V3]651.2(2)2396.05(19)
Calculated density [g·cm−3]1.3581.437
Crystal size [mm3]0.21×0.20×0.190.21×0.20×0.19
μ [mm−1]0.1060.111
S1.0461.028
Limiting indices−8 ≤ h ≤ 9,−20 ≤ h ≤ 14,
−9 ≤ k ≤ 9,−6 ≤ k ≤ 10,
−16 ≤ l ≤ 16−15 ≤ l ≤ 18
Reflections collected 63529815
Unique reflections29494221
Parameters172344
Restraints50
Rint0.0310.0477
R1, wR2 [all data]0.0655, 0.14970.0970, 0.1925
R1, wR2 [I>2σ(I)]0.0564, 0.14200.0633, 0.1649
Largest diff.peak and hole [e·Å−3]0.412, −0.3020.422, −0.321
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